Citral derivatives

ABSTRACT

Improved citral derivatives, and fragrances and flavorings including the derivatives, that have a longer useful shelf life than citral and/or fragrances and flavorings including citral, are disclosed. In particular, the derivatives maintain the fragrance characteristics of citral, while lowering the allergic properties, and lemony flavors and fragrances with a longer shelf-life than citral, are disclosed. Also disclosed are methods of making the derivatives, and articles of manufacture including the derivatives. In one embodiment, the derivatives are prepared by replacing one or more double bonds in citral with a cyclopropyl group, which can be unsubstituted, or substituted with one or two lower alkyl, preferably methyl groups. The alkyl groups can optionally be substituted, for example, with electron donating groups, electron with drawing groups, groups which increase the hydrophilicity or hydrophobocity, and the like. In another embodiment, the derivatives are prepared by replacing the aldehyde group in citral with a nitrile, methyl ether or acetal group. The acetal groups can provide the compounds with a long lasting flavor or fragrance, where the acetals slowly hydrolyze to provide the aldehyde group in citral. In some embodiments, both the aldehyde and at least one of the double bond functional groups are both derivatized as described herein. Examples of suitable articles of manufacture include candles, air fresheners, perfumes, disinfectant compositions, hypochlorite (bleach) compositions, beverages such as beer and soda, denture cleanser tablets and flavored orally-delivered products such as lozenges, candies, and the like.

FIELD OF THE INVENTION

The present invention relates generally to the field of flavorings andfragrances. More particularly, the present invention relates to citralderivatives that provide beverages and other food products, as well asperfumes and other fragrant articles with a lemony scent, while at thesame time overcoming the stability limitations of the native citralcompound. This application is a continuation of PCT/US02/26446, filed 20Aug. 2002; which claims priority to U.S. Provisional Application Nos.60/377,914, filed May 3, 2002; 60/389,298, filed Jun. 17, 2002;60/355,052, filed Feb. 7, 2002; 60/342,150, filed Dec. 19, 2001,60/348,580, filed Jan. 15, 2002, PCT/US02/22120, filed Jul. 12, 2002 andPCT/US02/22441, filed Jul. 12, 2002, the contents of each of which arehereby incorporated by reference.

BACKGROUND OF THE INVENTION

Citral (3,7 dimethyl 2,6 octadienal) is a major component of lemonsmell, and has the sweet-acidulated character of natural lemon. Forlargely historical reasons, lemon smell has become associated withfreshness and cleanliness, both in drinks and in household products, andin fragrances and flavorings, generally. Lemon drinks, whether naturalor synthetic, are naturally acid, which causes rapid degradation ofcitral to unpleasant-smelling products like cresol. This means that theshelf life of lemonade is correspondingly short, creating an expensivelogistical problem. In household products, the problem is of a differentnature. In order to associate bacteriological cleanliness with the smellof lemon these products frequently use lemon-scented bleach(hypochlorite). Citral is unstable in bleach, and cannot therefore beused. Instead, its nitrile analogue, geranyl nitrile, with its lesssatisfactory oily-metallic lemon note has to be used.

The chemical instability of citral is largely due to the two doublebonds and an aldehyde group, all of which are potentially susceptible toreaction, particularly when used in harsh environments, such aslemon-scented bleach. It would be desirable to develop citralderivatives with improved useful lifetimes, and, preferably, improvedodor intensity, while maintaining the lemon note of citral. The presentinvention provides such citral derivatives.

SUMMARY OF THE INVENTION

Improved fragrances and flavorings that have a longer useful shelf lifethan citral are disclosed. In particular, citral derivatives thatmaintain the fragrance characteristics and lemony flavor of citral,while lowering the allergic properties, providing a longer shelf-lifethan citral, and/or increasing the odor intensity relative to citral aredisclosed. Also disclosed are methods of making the derivatives, andarticles of manufacture including the derivatives.

In one embodiment, the citral derivatives are prepared by replacing oneor more double bonds in the parent molecule with a cyclopropyl group,which can be unsubstituted, or substituted with one or two lower alkyl,preferably methyl groups. The alkyl groups can optionally besubstituted, for example, with electron donating groups, electronwithdrawing groups, groups which increase the hydrophilicity orhydrophobocity, and the like. In another embodiment, the derivatives areprepared by replacing one or more aldehyde groups in citral with anitrile, methyl ether or acetal group. The acetal groups can provide thecompounds with a long lasting flavor or fragrance, where the acetalsslowly hydrolyze to provide the parent aldehyde compounds. In someembodiments, suitable derivatives are prepared such that the aldehydeand at least one double bond functional group is derivatized asdescribed herein.

Examples of suitable articles of manufacture include candles, airfresheners, perfumes, disinfectant compositions, hypochlorite (bleach)compositions, beverages such as beer and soda, denture cleanser tabletsas described, for example, in U.S. Pat. No. 5,571,519, the contents ofwhich are hereby incorporated by reference in their entirety, andflavored orally-delivered products such as lozenges, candies, and thelike.

DETAILED DESCRIPTION OF THE INVENTION

Improved citral derivatives, which can be used, for example, asfragrances and flavorings that have a longer useful shelf life thancitral, are disclosed. The citral derivatives have a similar odor tocitral and also have improved physical and/or chemical propertiesrelative to citral. These improved properties include increasedstability to high pH, low pH, improved half-life, lower likelihood ofcausing allergic reactions, and/or increased odor intensity.

The compounds of Formulas 2-4 described herein have one or more doublebonds of citral or the citral derivatives in Formula 1 replaced with asuitable three membered ring. The compounds, and mixtures thereof, arestable in various media in which citral itself is relatively unstableand also have unstable, and also have odor characteristics which arevery similar to that of citral. The odor of the compounds of formulas2-4, or mixtures thereof, possess the same fresh-citrus connotation ascitral.I. Improved Citrals

Formula 1 represents citral and citral derivatives that can be modifiedusing the chemistry described herein to replace one or both of thedouble bonds with appropriate ring structures, thus improving thevarious physical and/or chemical properties of the molecule. In Formula1, citral is depicted where X is —C(═O)H, R₁₋₄ are H, and R₅ and R₆ aremethyl. However, R₁₋₆ can be, independently, H, C₁₋₅ alkyl, substitutedC₁₋₅ alkyl, halo, hydroxy, thiol, thioether, amine, carboxylic acid,ester, nitro, cyano, isocyano, sulfonic acid, urea, and thiourea, wherethe substituents on the alkyl groups are selected from halo, hydroxy,thiol, thioether, amine, carboxylic acid, ester, nitro, cyano, isocyano,sulfonic acid, urea, thiourea, and the like. X can be —C(═O)H,—OCH₃,—C(OR)₂H, —CN, —C(═O)CH₃,—NC, —C≡C— (alkyne), oxime, C(═O)OR⁷ (where R⁷is a C₁₋₅ alkyl), or an oxalate ester, where R is H, C₁₋₅ alkyl or C₁₋₅substituted alkyl. The attachment to X shows that the double bondincluding X can be in the E or Z configuration. In one embodiment, thedouble bond adjacent to the aldehyde group in citral is saturated (i.e.,citronellal), and the derivatives are the same but for the saturateddouble bond at this position.

Formulas 2-4 below represent citral derivatives as described herein,where one or both of the double bonds are replaced with a suitable threemembered ring.

wherein:

Z is O, S, or C(R)₂,

R is H, C₁₋₅ alkyl, such as methyl, or C₁₋₅ substituted alkyl, and

X is —C(═O)H, —OCH₃, —C(OR)₂H, —CN, —C(═O)CH₃,—NC, —C≡C— (alkyne),oxime, C(═O)OR⁷ (where R⁷ is a C₁₋₅ alkyl), or an oxalate ester, whereR₁₋₆ are as described above with respect to Formula 1, and in Formula 3,the attachment of the double bond to X indicates that the double bondcan exist in the E or Z configuration. The single bond attachments to X,R¹, R², R⁵ and R⁶ are not intended to reflect any specificstereochemistry.

In one embodiment of Formulas 2-4, R₁₋₄ represent hydrogen, R₅₋₆represent methyl, and Z represents C(R)₂. In this embodiment, it ispreferred that one or more R groups are methyl, with the other R groupsrepresenting hydrogen.

In Formulas 2-4, where the molecule includes two Z groups, one Z canrepresent saturation at both carbons to which it is bound (i.e., nodouble bond or cyclopropane, oxirane or thiirane ring), so long as one Zis O, S or C(R)₂.

Citral can be cyclopropanated in one or both of the positions,corresponding to the two double bonds of the molecule. Cyclopropanationof the double bond alpha to the carbonyl provides four possiblediastereomers, (R,R), (R,S), (S,R) and (S,S). Cyclopropanation of thedouble bond of the isoprene unit provides two stereoisomers for each ofthe E and Z isomers of the double bond alpha to the carbonyl, for atotal of four isomers. Dicyclopropanation provides eight steriosomericforms, including all four diastereomers from the cyclopropanation of thedouble bond alpha to the carbonyl coupled with the R stereoisomer fromthe cyclopropanation of the double bond in the isoprene unit, and allfour diastereomers coupled with the S stereoisomer. The double bond inthe isoprene unit of citronnelal can also be cyclopropanated to yieldtwo stereoisomers.

The cyclopropanation reaction can be performed to exhaustion, providingthe dicyclopropanated product, or can be performed stepwise, yielding amixture of mono and dicyclopropanated products. The mono- anddi-cyclopropanated products can be separated on the basis of differentphysical and chemical properties. Diastereomeric forms can be separatedon the basis of different properties as well, such as different boilingpoints and/or crystallization conditions, as is known in the art.Stereoisomers can be isolated using known techniques, such as columnchromatography using a chiral solid phase, enzymatic degradation, andreversible formation of diastereomers and separation of thediastereomeric forms, as is known in the art. The presence of thealdehyde functionality permits the rapid and reversible formation ofdiastereomers by reaction with chiral alcohols to form hemiacetals oracetals, which can be hydrolyzed to reform the aldehyde functionality.Suitable chiral alcohols are well known to those of skill in the art.Accordingly, should it be desired to isolate particular stereoisomers ordiastereomers, it would be routine in the art to do so.

While the disclosure is not limited to the following drawing, allsixteen stereoisomeric forms of mono- and di-cyclopropropanated citralderivatives, and both stereoisomeric forms of cyclopropanatedcitronnelal are shown below. The replacement of double bonds withcyclopropane rings in other compounds will likewise often result in theformation of stereoisomers and/or diastereomers, and individualstereoisomers and/or diastereomers can similarly be isolated usingconventional separation techniques. Such stereoisomers and/ordiastereomers are intended to be within the scope of the inventiondescribed herein.

The cyclopropane rings can include a CH₂ moiety, or can be substitutedwith one or two C₁₋₅ alkyl (i.e., methyl) groups. The methyl or dimethylanalogues have a tunnelling vibrational spectrum that more closelymatches citral than the unsubstituted cyclopropane derivatives, and hasa sweeter smell than the unsubstituted cyclopropyl derivatives.

The citral derivatives described herein include derivatives in which oneor both of the double bonds is replaced with a (unsubstituted, monoalkylor dialkyl, where alkyl can be substituted or unsubstituted, and ispreferably methyl) cyclopropyl group. The compounds can include, incombination with or in place of a cyclopropyl group, the replacement ofthe aldehyde with a methyl ether, a nitrile or an acetal group.

II. Methods for Preparing the Citral Derivatives

The citral derivatives of Formulas 2-4 can be prepared using any of thecitral derivatives described above in Formula 1, to the extent that thesynthetic route is not incompatible with any of the substituents thatmay be present. In one embodiment, citral (or citronellal) is used as astarting material to prepare various citral (or citronellal) derivativesdescribed in Formulas 2-4 where R₁₋₄ are hydrogen and R₅₋₆ are methyl.

The synthesis of methyl, dimethyl or unsubstituted cyclopropanederivatives is well known to those of skill in the art, and involves,for example, bromoform reaction to form the dibromocyclopropanederivative, followed by stoichiometric reaction with methyl lithium. Thealdehyde group is typically protected as an acetal during the reaction,and deprotected as desired after the reactions take place. In oneembodiment, however, the acetals (for example, dimethyl, diethyl, orethylene glycol) are not deprotected to the aldehyde, such that theflavoring or fragrance includes a portion or entirely the acetals. Theacetals can then slowly hydrolyze over time, releasing the lemonscent/flavoring. Alternatively, citral derivatives, including one or twocyclopropane rings, can also include a nitrile or methyl ether group asa replacement for the aldehyde group.

These simple procedures yield derivatives of citral with odor profilesclose to citral itself, with greater potency and with far greater acidand bleach stability since the unstable feature, namely the double bond,has been removed.

The same applies to epoxide (OX) and thiirane (TH) rings, shown in theformulas above where Z is O or S. Not counting mixed C═C double bondreplacements and stereoisomers, this generates 9 possible molecules fromcitral alone, all readily accessible in one or two step syntheses fromcitral itself by processes well known in the art, such as:

Cyclopropanyl replacement: Simmons-Smith cyclopropanation of thealdehyde or corresponding alcohol, followed by periodinane oxidation forthe latter to give the aldehyde¹

Oxiranyl replacement: m-chloroperbenzoic acid epoxidation²

Thiiranyl replacement: bromination of double bond on Amberlite, followedby S′—substitution in sodium sulfides³

Aldehyde Replacement with Nitrile

The replacement of aldehyde with nitrile is well known in the art, anddescribed, for example, in U.S. Patent No. 5,892,092. The '092 patentteaches a process for forming nitrites from aldehydes. Citralderivatives can further be prepared in which one or more a double bondsare converted to (unsubstituted, methyl or dimethyl) cyclopropylderivatives that also include a nitrile group in place of the aldehydeusing the chemistry described above.

III. Articles of Manufacture Including the Citral Derivatives

The citral derivatives can be included in virtually any article ofmanufacture that can include citral, or for that matter, other lemonfragrances, whether natural or artificial. Examples include bleach,detergents, flavorings and fragrances, beverages, including alcoholicbeverages, and the like. The citral derivatives can be used inapplications like soaps, shampoos, body deodorants and antiperspirants,solid or liquid detergents for treating textiles, fabric softeners,detergent compositions and/or all-purpose cleaners for cleaning dishesor various surfaces, for both

1 Vogel's textbook of practical organic chemistry 5th edition (1989) pp1106-1108

2 Ibid, pp 1127-1129

3 Choi, J. et al. (1995) Bull. Korean. Chem. Soc., 16, 189-190Convenient Synthesis of Symmetrical Sulfides from Alkyl Halides andEpoxides household and industrial use. Of course, the use of thecompounds is not limited to the above-mentioned products, as they beused in other current uses in perfumery, namely the perfuming of soapsand shower gels, hygiene or hair-care products, as well as of bodydeodorants, air fresheners and cosmetic preparations, and even in fineperfumery, namely in perfumes and colognes. These uses are described inmore detail below.

Perfume Compositions

The compounds can be used as perfuming ingredients, as single compoundsor as mixture thereof, preferably at a range of at least about 30% byweight of the perfume composition, more preferably at a range of atleast about 60% by weight of the composition. The compounds can even beused in their pure state or as mixtures, without added components. Theolfactive characteristics of the individual compounds are also presentin mixtures thereof, and mixtures of these compounds can be used asperfuming ingredients. This may be particularly advantageous whereseparation and/or purification steps can be avoided by using compoundmixtures.

In all cited applications, the citral derivatives can be used alone orin admixture with other perfuming ingredients, solvents or adjuvants ofcurrent use in the art. The nature and the variety of theseco-ingredients do not require a more detailed description here, which,moreover, would not be exhaustive, and the person skilled in the artwill be able to choose the latter through its general knowledge and as afunction of the nature of the product to be perfumed and of the desiredolfactive effect.

These perfuming ingredients typically belong to chemical classes asvaried as alcohols, aldehydes, ketones, esters, ethers, acetates,nitrites, terpene hydrocarbons, sulfur- and nitrogen-containingheterocyclic compounds, as well as essential oils of natural orsynthetic origin. A large number of these ingredients described inreference textbooks such as the book of S. Arctander, Perfume and FlavorChemicals, 1969, Montclair, N.J., USA, the contents of which are herebyincorporated by reference in its entirety, or its more recent versions,or in other works of similar nature.

The proportions in which the citral derivatives can be incorporated inthe various products vary within a large range of values. These valuesdepend on the nature of the article or product that one desires toperfume and the odor effect searched for, as well as on the nature ofthe co-ingredients in a given composition when the compounds are used inadmixture with perfuming co-ingredients, solvents or adjuvants ofcurrent use in the art.

As an example, the citral derivatives are typically present atconcentrations between about 0.1 and about 10%, or even more, by weightof these compounds relative to the weight of the perfuming compositionin which they are incorporated. Far lower concentrations than thosementioned above can be used when the compounds are directly applied forperfuming the various consumer products cited beforehand.

The compounds are relatively stable in typically aggressive media forperfumes. Accordingly, they can be used in detergents containingbleaching agents and activators such as, for example,tetraacetylethylenediamine (TAED), hypohalites, in particularhypochlorite, peroxygenated bleaching agents such as, for example,perborates, etc. The compounds can also be used in body deodorants andantiperspirants, for example, those containing aluminum salts. Theseembodiments are described in more detail below.

Conventional Detergent Ingredients

In addition to the derivatives described herein, the compositions hereininclude a detersive surfactant and optionally, one or more additionaldetergent ingredients, including materials for assisting or enhancingcleaning performance, treatment of the substrate to be cleaned, or tomodify the aesthetics of the detergent composition (e.g., perfumes,colorants, dyes, etc.). The following are illustrative examples ofdetersive surfactants and other detergent ingredients.

Detersive Surfactants Non-limiting examples of synthetic detersivesurfactants useful herein typically at levels from about 0.5% to about90%, by weight, include the conventional C₁₁₋₁₈ alkyl benzene sulfonates(“LAS”) and primary, branch-chain and random C₁₀₋₂₀ alkyl sulfates(“AS”), the C₁₀₋₁₈ secondary (2,3) alkyl sulfates of the formulaCH₃(CH₂)_(x)(CH(CH₃)OSO₃ ⁻M⁺) and CH₃(CH₂)_(y) (CH(CH₂CH₃)OSO₃ ⁻M⁺)wherein x and y are integers and wherein each of x and (y+1) is leastabout 7, preferably at least about 9, and M is a water-solubilizingcation, especially sodium, unsaturated sulfates such as oleyl sulfate,the C₁₀₋₁₈ alkyl alkoxy sulfates (“AEx S”; especially EO 1-7 ethoxysulfates), C₁₀₋₁₈ alkyl alkoxy carboxylates (especially the EO 1-5ethoxycarboxylates), the C₁₀₋₁₈ glycerol ethers, the C₁₀₋₁₈ alkylpolyglycosides and their corresponding sulfated polyglycosides, andC₁₂₋₁₈ alpha-sulfonated fatty acid esters. If desired, the conventionalnonionic and amphoteric surfactants such as the C₁₂₋₁₈ alkyl ethoxylates(“AE”) including the so-called narrow peaked alkyl ethoxylates and C₆₋₁₂alkyl phenol alkoxylates (especially ethoxylates and mixedethoxy/propoxylates), C₁₂₋₁₈ betaines and sulfobetaines (“sultaines”),C₁₀₋₁₈ amine oxides, and the like, can also be included in the overallcompositions. The C₁₀₋₁₈ N-alkyl polyhydroxy fatty acid amides can alsobe used. Typical examples include the C₁₂₋₁₈ N-methylglucamides. See WO9,206,154. Other sugar-derived surfactants include the N-alkoxypolyhydroxy fatty acid amides, such as C₁₀₋₁₈ N-(3-methoxypropyl)glucamide. The N-propyl through N-hexyl C₁₂₋₁₈ glucamides can be usedfor low sudsing. C₁₀₋₂₀ conventional soaps may also be used, howeversynthetic detergents are preferred. If high sudsing is desired, thebranched-chain C₁₀₋₁₆ soaps may be used. Mixtures of anionic andnonionic surfactants are especially useful. Other conventional usefulsurfactants are listed in standard texts. See also U.S. Pat. No.3,664,961 to Norris.

Preferred compositions incorporating only synthetic detergents have adetergent level of from about 0.5% to 50%. Compositions containing soappreferably comprise from about 10% to about 90% soap.

Although the detergent compositions herein can only only detersivesurfactants and the citral derivative(s), the compositions preferablycontain other ingredients commonly used in detergent products.

Builders

Detergent builders can optionally be included in the compositions hereinto assist in controlling mineral hardness. Inorganic as well as organicbuilders can be used. Builders are typically used in fabric launderingcompositions to assist in the removal of particulate soils.

The level of builder can vary widely depending upon the end use of thecomposition and its desired physical form. When present, thecompositions will typically comprise at least about 1% builder. Liquidformulations typically comprise from about 5% to about 50%, moretypically about 5% to about 30%, by weight, of detergent builder.Granular formulations typically comprise from about 10% to about 80%,more typically from about 15% to about 50% by weight, of the detergentbuilder. Lower or higher levels of builder, however, are not meant to beexcluded.

Inorganic or detergent builders include, but are not limited tophosphate builders such as, the alkali metal, ammonium andallanolammonium salts of polyphosphates (exemplified by thetripolyphosphates, pyrophosphates, and glassy polymericmeta-phosphates), phosphonates, and phytic acid, and non-phosphorousbuilders such as silicates, carbonates (including bicarbonates andsesquicarbonates), sulphates, and aluminosilicates. Non-phosphatebuilders are required in some locales.

Organic builders suitable for use herein include polycarboxylatebuilders such as disclosed in U.S. Pat. No. 3,308,067 to Diehl; U.S.Pat. No. 4,144,226 to Crutchfield and U.S. Pat. No. 4,246,495 toCrutchfield.

Soil Release Agents

Soil Release agents are desirably used in laundry detergents of theinstant invention. Suitable soil release agents include those of U.S.Pat. No. 4,968,451 to Scheibel and Gosselink: such ester oligomers canbe prepared by (a) ethoxylating allyl alcohol, (b) reacting the productof (a) with dimethyl terephthalate (“DMT”) and 1,2-propylene glycol(“PG”) in a two-stage transesterification/oligomerization procedure and(c) reacting the product of (b) with sodium metabisulfite in water; thenonionic end-capped 1,2-propylene/polyoxyethylene terephthalatepolyesters of U.S. Pat. No. 4,711,730 to Gosselink et al, for examplethose produced by transesterification/oligomerization ofpoly(ethyleneglycol) methyl ether, DMT, PG and poly(ethyleneglycol)(“PEG”); the partly- and fully-anionic-end-apped oligomeric esters ofU.S. Pat. No. 4,721,580 to Gosselink, such as oligomers from ethyleneglycol (“EG”), PG, DMT and Na-3,6-dioxa-8-hydroxyoctanesulfonate; thenonionic-capped block polyester oligomeric compounds of U.S. Pat. No.4,702,857 to Gosselink, for example produced from DMT, Me-capped PEG andEG and/or PG, or a combination of DMT, EG and/or PG, Me-capped PEG andNa-dimethyl-5-sulfoisophthalate; and the anionic, especially sulfoaroyl,end-capped terephthalate esters of U.S. Pat. No. 4,877,896 to Maldonado,Gosselink et al, the latter being typical of SRA's useful in bothlaundry and fabric conditioning products, an example being an estercomposition made from m-sulfobenzoic acid monosodium salt, PG and DMToptionally but preferably further comprising added PEG, e.g., PEG 3400.Another preferred soil release agent is a sulfonated end-capped typedescribed in U.S. Pat. No. 5,415,807.

Other Optional Ingredients

The compositions herein can contain other ingredients such as enzymes,bleaches, fabric softening agents, dye transfer inhibitors, sudssuppressors, and chelating agents, all well known within the art.

For purposes of defining detergent compositions of the presentinvention, the pH of the detergent composition is that which is measuredat 1% concentration of the detergent composition in distilled-water at20° C. The detergent compositions herein have a pH of from about 7.1 toabout 13, more typically from about 7.5 to about 9.5 for liquiddetergents and from about 8 to about 12 for granular detergents.

Formulation with Detergents With or Without Conventional PerfumeryMaterials

While the derivatives described herein can be used alone and simplymixed with essential detergent ingredient, most notably surfactant, theycan also be desirably combined into three-part formulations whichcombine (a) a non-fragranced detergent base comprising one or moresynthetic detergents and (b) one or more of the derivatives describedherein. In one embodiment, both aldehydes and acetals are present, suchthat the aldehydes provide desirable in-package and in-use (wash-time)fragrance, while the acetals provide a long-term fragrance to thelaundered textile fabrics.

In formulating the present detergents, the fully-formulated fragrancecan be prepared using numerous known odorant ingredients of natural orsynthetic origin. The range of the natural raw substances can embracenot only readily-volatile, but also moderately-volatile andslightly-volatile components and that of the synthetics can includerepresentatives from practically all classes of fragrant substances, aswill be evident from the following illustrative compilation: naturalproducts, such as tree moss absolute, basil oil, citrus fruit oils (suchas bergamot oil, mandarin oil, etc.), mastix absolute, myrtle oil,palmarosa oil, patchouli oil, petitgrain oil Paraguay, wormwood oil,alcohols, such as famesol, geraniol, linalool, nerol, phenylethylalcohol, rhodinol, cinnamic alcohol, aldehydes, such as citral,Helional™, alpha-hexyl-cinnamaldehyde, hydroxycitronellal, Lilial™(p-t-butyl-alpha-methyldihydrocinnamaldehyde), methylaonylacetaldehyde,ketones, such as allylionone, alpha-ionone, beta-ionone, isoraldein(isomethyl-alpha-ionone), methylionone, esters, such as allylphenoxyacetate, benzyl salicylate, cinnamyl propionate, citronellylacetate, citronellyl ethoxolate, decyl acetate, dimethylbenzylcarbinylacetate, dimethylbenzylcarbinyl butyrate, ethyl acetoacetate, ethylacetylacetate, hexenyl isobutyrate, linalyl acetate, methyldihydrojasmonate, styrallyl acetate, vetiveryl acetate, etc., lactones,such as gamma-undecalactone, various components often used in perfumery,such as musk ketone, indole, p-menthane-8-thiol-3-one, andmethyl-eugenol. Likewise, any conventional fragrant acetal or ketalknown in the art can be added to the present composition as an optionalcomponent of the conventionally formulated perfume (c). Suchconventional fragrant acetals and ketals include the well-known methyland ethyl acetals and ketals, as well as acetals or ketals based onbenzaldehyde, those comprising phenylethyl moieties, or more recentlydeveloped specialties such as those described in a United States Patententitled “Acetals and Ketals of Oxo-Tetralins and Oxo-Indanes, see U.S.Pat. No. 5,084,440. Of course, other recent synthetic specialties can beincluded in the perfume compositions for fully-formulated detergents.These include the enol ethers of alkyl-substituted oxo-tetralins andoxo-indanes as described in U.S. Pat. No. 5,332,725; or Schiff Bases asdescribed in U.S. Pat. No. 5,264,615. It is preferred that thepro-fragrant material be added separately from the conventionalfragrances to the detergent compositions of the invention.

Formulation with Other Special-Purpose Fragrance Delivering Compounds

Detergents including the derivatives described herein may further,optionally, if desired, contain other known compounds having thecapability to enhance substantivity of a fragrance. Such compoundsinclude, but are not limited to, the aluminium alkoxides such asisobutylaluminium diferanylate as disclosed in U.S. Pat. No. 4,055,634;or the known titanate and zirconate esters or oligoesters of fragrantmaterials such as those disclosed in U.S. Pat. No. 3,947,574, and U.S.Pat. No. 3,779,932, the contents of each of which are herebyincorporated by reference in their entirey. When using suchorganoaluminum, organotitanium or organozinc derivatives, they may beincorporated into the present formulations at their art-known levels.

Beverage Compositions

The citral derivatives described herein can be incorporated intobeverages and impart various flavorings to the beverages. The beveragecomposition can be a cola beverage composition, and can also be coffee,tea, dairy beverage, fruit juice drink, orange drink, lemon-lime drink,beer, malt beverages, or other flavored beverage. The beverages can bein liquid or powdered form.

The beverage compositions can also include one or more flavoring agents;artificial colorants; vitamin additives; preservatives; caffeineadditives; water; acidulants; thickeners; buffering agents; emulsifiers;and or fruit juice concentrates.

Artificial colorants which may be used include caramel color, yellow 6and yellow 5. Useful vitamin additives include vitamin B2, vitamin B6,vitamin B12, vitamin C (ascorbic acid), niacin, pantothenic acid, biotinand folic acid. Suitable preservatives include sodium or potassiumbenzoate. Salts which may be used include sodium, potassium andmagnesium chloride. Exemplary emulsifiers are gum arabic and purity gum,and a useful thickener is pectin. Suitable acidulants include citric,phosphoric and malic acid, and potential buffering agents include sodiumand potassium citrate.

In one embodiment, the beverage is a carbonated cola beverage. The pH isgenerally about 2.8 and the following ingredients can be used to makethe syrup for these compositions: Flavor Concentrate, including one ormore of the derivatives described herein (22.22 ml), 80% Phosphoric Acid(5.55 g), Citric Acid (0.267 g), Caffeine (1.24 g), artificialsweetener, sugar or corn syrup (to taste, depending on the actualsweetener) and Potassium Citrate (4.07 g). The beverage composition canbe prepared, for example, by mixing the foregoing syrup with carbonatedwater in a proportion of 50 ml syrup to 250 ml of carbonated water.

In another embodiment, the beverage is a beer or malt beverage.Preferred flavorings for beer and malt beverages include lemon, lime andlemon-lime. Advantageously, the flavorings include citral derivatives inwhich one of both of the double bonds are replaced with a cyclopropanegroup, where the cyclopropane groups can, independently, beunsubstituted, or include one or two alkyl or substituted alkyl groups,preferably methyl groups. The amount of flavoring can be adjustedaccording to taste.

Orally-Delivered Products

Flavored food and pharmaceutical compositions including one or more ofthe derivatives described herein can also be prepared. The derivativescan be incorporated into conventional foodstuffs using techniques wellknown to those of skill in the art. Alternatively, the derivatives canbe incorporated within polymeric particles, which can, in turn, bedispersed within and/or over a surface of an orally-deliverable matrixmaterial, which is usually a solid or semi-solid substrate. When used inchewable compositions, the derivatives can be released into theorally-deliverable polymeric matrix material as the composition ischewed and held in the mouth, thus prolonging the flavor of thecomposition. In the case of dried powders and mixes, the flavor can bemade available as the product is consumed or be released into the matrixmaterial as the composition is further processed. When two flavors arecombined with the polymeric particles, the relative amounts of theadditives can be selected to provide simultaneous release and exhaustionof the compounds.

In one embodiment, the flavored composition includes anorally-deliverable matrix material; a plurality of water insolublepolymeric particles dispersed in the orally-deliverable matrix material,where the polymeric particles individually defme networks of internalpores and are non-degradable in the digestive tract; and one or morederivatives as described herein entrapped within the internal porenetworks. The derivatives are released as the matrix is chewed,dissolved in the mouth, or undergoes further processing selected fromthe group consisting of liquid addition, dry blending, stirring, mixing,heating, baking, and cooking. The orally-deliverable matrix material canbe selected from the group consisting of gums, latex materials,crystallized sugars, amorphous sugars, fondants, nougats, jams, jellies,pastes, powders, dry blends, dehydrated food mixes, baked goods,batters, doughs, tablets, and lozenges.

Chewing Gum

A flavorless gum base can be combined with a citral or other suitablederivative as described herein to a desired flavor concentration.Typically, a blade mixer is heated to about 110 F, the gum base ispreheated so that it is softened, and the gum base is then added to themixer and allowed to mix for approximately 30 seconds. The flavoredderivative is then added to the mixer and mixed for a suitable amount oftime. The gum can be then removed from the mixer and rolled to stickthickness on waxed paper while warm.

Time Release Formulations

In one embodiment, the derivatives described herein are incorporatedinto a system which can release a fragrance in a controlled manner.These include substrates such as air fresheners, laundry detergents,fabric softeners, deodorants, lotions, and other household items. Thefragrances are generally one or more derivatives of essential oils asdescribed herein, each present in different quantities. U.S. Pat. No.4,587,129, the contents of which are hereby incorporated by reference intheir entirety, describes a method for preparing gel articles whichcontain up to 90% by weight of fragrance or perfime oils. The gels areprepared from a polymer having a hydroxy (lower alkoxy) 2-alkeneoate, ahydroxy (lower alkoxy) lower alkyl 2-alkeneoate, or a hydroxy poly(lower alkoxy) lower alkyl 2-alkeneoate and a polyethylenicallyunsaturated crosslinking agent. These materials have continuous slowrelease properties, i.e., they release the fragrance componentcontinuously over a long period of time. Advantageously, all or aportion of those derivatives that include an aldehyde group can bemodified to include an acetal group, which can cause the formulations torelease fragrance over a period of time as the acetal hydrolyzes to formthe aldehyde compound.

The invention will now be illustrated with reference to the followingnon-limiting example.

EXAMPLE 1 Preparation and Flavor Characteristics of a CyclopropanatedCitral Derivative

Cyclopropanation of Citral to Produce Citral-6,7-Cyclopropane.

The following experimental was based on a well-known method forcyclopropanating olefins, and was conducted numerous times with variousstoichiometric equivalents of the cyclopropanation reagents. Optimumresults for synthesizing the above-identified mono-cyclopropanatedcitral derivative were obtained using the amounts shown below. Attemptsto increase relative amounts of reagents resulted in the formation of asignificant amount of side products. However, this reaction has not beenoptimized. The use of less than a stoichiometric amount of thediethylzinc and diiodomethane reactants might be advisable if theseparation of citral and citral-6,7-cyclopropane were optimized.However, since the separation was not optimized, the cyclopropanationreaction was allowed to proceed to completion. The reactions wereconducted behind a blast shield due to the reported possible explosivenature of these reactions. It is believed that cyclopropanations usingthese reaction conditions may be problematic if the diiodomethane isadded too quickly to the reaction mixture

Citral-6,7-Cyclopropane

To an oven dried 500 mL round bottomed flask was added1,2-dichloroethane (85 mL) under a nitrogen atmosphere. Diethylzinc (30mL, 1M in hexanes) was added, and then diiodomethane (15 g) wasintroduced dropwise over 1 hour. Following stirring for 30 mins (a whiteprecipitate formed) citral (1.1 g) was added and the reaction wasstirred overnight at room temperature.

The reaction mixture was poured into a potassium carbonate solution (100mL, 20%) and then filtered through a pad of Celite® in a sinteredfunnel. The organic layer was separated and dried over sodium sulfate.Filtration of the drying agent, concentration and flash columnchromatography with dichloromethane as eluant gave the title compound.

The compound was tasted by two experienced flavorists, who both declaredit lemony.

Having hereby disclosed the subject matter of the present invention, itshould be apparent that many modifications, substitutions, andvariations of the present invention are possible in light thereof. It isto be understood that the present invention can be practiced other thanas specifically described. Such modifications, substitutions andvariations are intended to be within the scope of the presentapplication.

1. A perfume composition comprising a citral derivative having one ofthe following formulas:

wherein R₁₋₆ are, independently, selected from the group consisting ofH, C₁₋₅ alkyl, substituted C₁₋₅ alkyl, halo, hydroxy, thiol, thioether,amine, carboxylic acid, ester, nitro, cyano, isocyano, sulfonic acid,urea and thiourea, Z is S, C(R)₂, or saturation at the two carbons towhich it is bound, provided that at least one Z is S or C(R)₂, R is,independently, H, C₁₋₅ alkyl or C₁₋₅ substituted alkyl, X is —C(═O)H,—OCH₃, —C(OR)₂H, —CN, —C(═O)CH₃,—NC, —C≡C—R (alkyne), oxime, C(═O)OR⁷(where R⁷ is a C₁₋₅ alkyl), or an oxalate ester, where R is H, C₁₋₅alkyl or C₁₋₅ substituted alkyl, wherein the substituents on thesubstituted alkyl groups are selected from the group consisting of halo,hydroxy, thiol, thioether, amine, carboxylic acid, ester, nitro, cyano,isocyano, sulfonic acid, urea, and thiourea, and wherein the double bondattached to X can be in the E or Z configuration.
 2. The perfumecomposition of claim 1, wherein the citral derivative includes at leastone C(R)₂ group, and at least one R in the C(R)₂ group is methyl.
 3. Theperfume composition of claim 1, wherein the citral derivative includesat least one C(R)₂ group, and both R groups in at least one C(R)₂ groupare methyl.
 4. The perfume composition of claim 1, wherein the X groupin the citral derivative is a nitrile, methyl ether or acetal group. 5.The perfume composition of claim 1, wherein the X group in the citralderivative is —C(═O)H.
 6. The perfume composition of claim 1, whereinR₁₋₄ groups in the citral derivative are hydrogen.
 7. The perfumecomposition of claim 1, wherein R₅₋₆ groups in the citral derivative aremethyl.
 8. A perfume composition of claim 1, wherein the citralderivative is of Formula II, wherein X is —C(═O)H, R₁₋₄ are hydrogen andR₅₋₆ are methyl.
 9. A beverage comprising a citral derivative having oneof the following formulas:

wherein R₁₋₆ are, independently, selected from the group consisting ofH, C₁₋₅ alkyl, substituted C₁₋₅ alkyl, halo, hydroxy, thiol, thioether,amine, carboxylic acid, ester, nitro, cyano, isocyano, sulfonic acid,urea and thiourea, Z is S, C(R)₂, or saturation at the two carbons towhich it is bound, provided that at least one Z is S or C(R)₂, R is,independently, H, C₁₋₅ alkyl or C₁₋₅ substituted alkyl, X is —C(═O)H,—OCH₃, —C(OR)₂H, —CN, —C(═O)CH₃,—NC, —C≡C—R (alkyne), oxime, C(═O)OR⁷(where R⁷ is a C₁₋₅ alkyl), or an oxalate ester, where R is H, C₁₋₅alkyl or C₁₋₅ substituted alkyl, wherein the substituents on thesubstituted alkyl groups are selected from the group consisting of halo,hydroxy, thiol, thioether, amine, carboxylic acid, ester, nitro, cyano,isocyano, sulfonic acid, urea, and thiourea, and wherein the double bondattached to X can be in the E or Z configuration.
 10. The beverage ofclaim 9, wherein the citral derivative includes at least one C(R)₂group, and at least one R in the C(R)₂ group is methyl.
 11. The beverageof claim 9, wherein the citral derivative includes at least one C(R)₂group, and both R groups in at least one C(R)₂ group are methyl.
 12. Thebeverage of claim 9, wherein the X group in the citral derivative is anitrile, methyl ether or acetal group.
 13. The beverage of claim 9,wherein the X group in the citral derivative is —C(═O)H.
 14. Thebeverage of claim 9, wherein the R₁₋₄ groups in the citral derivativeare hydrogen.
 15. The beverage of claim 9, wherein the R₅₋₆ groups inthe citral derivative are methyl.
 16. The beverage of claim 9, whereinthe citral derivative is of Formula II, wherein X is —C(═O)H, R₁₋₄ arehydrogen and R₅₋₆ are methyl.
 17. The beverage of claim 9, wherein thebeverage is selected from the group consisting of beer, malt liquor,lemonade and cola.
 18. A flavored orally-delivered product comprising acitral derivative having one of the following formulas:

wherein R₁₋₆ are, independently, selected from the group consisting ofH, C₁₋₅ alkyl, substituted C₁₋₅ alkyl, halo, hydroxy, thiol, thioether,amine, carboxylic acid, ester, nitro, cyano, isocyano, sulfonic acid,urea and thiourea, Z is S, C(R)₂, or saturation at the two carbons towhich it is bound, provided that at least one Z is S or C(R)₂, R is,independently, H, C₁₋₅ alkyl or C₁₋₅ substituted alkyl, X is —C(═O)H,—OCH₃, —C(OR)₂H, —CN, —C(═O)CH₃,—NC, —C≡C—R (alkyne), oxime, C(═O)OR⁷(where R⁷ is a C₁₋₅ alkyl), or an oxalate ester, where R is H, C₁₋₅alkyl or C₁₋₅ substituted alkyl, wherein the substituents on thesubstituted alkyl groups are selected from the group consisting of halo,hydroxy, thiol, thioether, amine, carboxylic acid, ester, nitro, cyano,isocyano, sulfonic acid, urea, and thiourea, and wherein the double bondattached to X can be in the E or Z configuration.
 19. The flavoredorally-delivered product of claim 18, wherein the citral derivativeincludes at least one C(R)₂ group, and at least one R in the C(R)₂ groupis methyl.
 20. The flavored orally-delivered product of claim 18,wherein the citral derivative includes at least one C(R)₂ group, andboth R groups in at least one C(R)₂ group are methyl.
 21. The flavoredorally-delivered product of claim 18, wherein the X group in the citralderivative is a nitrile, methyl ether or acetal group.
 22. The flavoredorally-delivered product of claim 18, wherein the X group in the citralderivative is —C(═O)H.
 23. The flavored orally-delivered product ofclaim 18, wherein the R₁₋₄ groups in the citral derivative are hydrogen.24. The flavored orally-delivered product of claim 18, wherein the R₅₋₆groups in the citral derivative are methyl.
 25. The flavoredorally-delivered product of claim 18, wherein the citral derivative isof Formula II, wherein X is —C(═O)H, R₁₋₄ are hydrogen and R₅₋₆ aremethyl.
 26. A detergent or disinfectant composition comprising a citralderivative having one of the following formulas:

wherein R₁₋₆ are, independently, selected from the group consisting ofH, C₁₋₅ alkyl, substituted C₁₋₅ alkyl, halo, hydroxy, thiol, thioether,amine, carboxylic acid, ester, nitro, cyano, isocyano, sulfonic acid,urea and thiourea, Z is S, C(R)₂, or saturation at the two carbons towhich it is bound, provided that at least one Z is S or C(R)₂, R is,independently, H, C₁₋₅ alkyl or C₁₋₅ substituted alkyl, X is —C(═O)H,—OCH₃, —C(OR)₂H, —CN, —C(═O)CH₃,—NC, —C≡C—R (alkyne), oxime, C(═O)OR⁷(where R⁷ is a C₁₋₅ alkyl), or an oxalate ester, where R is H, C₁₋₅alkyl or C₁₋₅ substituted alkyl, wherein the substituents on thesubstituted alkyl groups are selected from the group consisting of halo,hydroxy, thiol, thioether, amine, carboxylic acid, ester, nitro, cyano,isocyano, sulfonic acid, urea, and thiourea, and wherein the double bondattached to X can be in the E or Z configuration.
 27. The detergent ordisinfectant composition of claim 26, wherein the citral derivativeincludes at least one C(R)₂ group, and at least one R in the C(R)₂ groupis methyl.
 28. The detergent or disinfectant composition of claim 26,wherein the citral derivative includes at least one C(R)₂ group, andboth R groups in at least one C(R)₂ group are methyl.
 29. The detergentor disinfectant composition of claim 26, wherein the X group in thecitral derivative is a nitrile, methyl ether or acetal group.
 30. Thedetergent or disinfectant composition of claim 26, wherein the X groupin the citral derivative is —C(═O)H.
 31. The detergent or disinfectantcomposition of claim 26, wherein the R₁₋₄ groups in the citralderivative are hydrogen.
 32. The detergent or disinfectant compositionof claim 26, wherein the R₅₋₆ groups in the citral derivative aremethyl.
 33. The detergent or disinfectant composition of claim 26,wherein the compound is of Formula II, wherein X is —C(═O)H, R₁₋₄ arehydrogen and R₅₋₆ are methyl.
 34. Citral derivatives having one of thefollowing formulas:

wherein R₁₋₆ are, independently, selected from the group consisting ofH, C₁₋₅ alkyl, substituted C₁₋₅ alkyl, halo, hydroxy, thiol, thioether,amine, carboxylic acid, ester, nitro, cyano, isocyano, sulfonic acid,urea and thiourea, Z is S or saturation at the two carbons to which itis bound, provided that at least one Z is S, X is —C(═O)H, —OCH₃,—C(OR)₂H, —CN, —C(═O)CH₃,—NC, —C≡C—R (alkyne), oxime, C(═O)OR⁷ (where R⁷is a C₁₋₅ alkyl), or an oxalate ester, where R is H, C₁₋₅ alkyl or C₁₋₅substituted alkyl, wherein the substituents on the substituted alkylgroups are selected from the group consisting of halo, hydroxy, thiol,thioether, amine, carboxylic acid, ester, nitro, cyano, isocyano,sulfonic acid, urea, and thiourea, and wherein the double bond attachedto X can be in the E or Z configuration.
 35. The citral derivatives ofclaim 34, wherein X is a nitrile, methyl ether or acetal group.
 36. Thecitral derivatives of claim 34, wherein X is —C(═O)H.
 37. The citralderivatives of claim 34, wherein R₁₋₄ are hydrogen.
 38. The citralderivatives of claim 34, wherein R₅₋₆ are methyl.
 39. The citralderivatives of claim 34 having the Formula 2, wherein X is —C(═O)H, R₁₋₄are hydrogen and R₅₋₆ are methyl.
 40. A composition comprising a citralderivative of claim 34, together with other perfuming ingredients,solvents, or adjuvants of current use in the art of perfumery.
 41. Thecomposition of claim 40, wherein the citral derivative is present in anamount of at least 30 percent by weight.
 42. The composition of claim40, wherein the citral derivative is present in an amount of at least 60percent by weight.
 43. A perfuming composition or perfumed articlecontaining as a perfuming ingredient a citral derivatives, or a mixtureof citral derivative, of claim
 34. 44. The perfuming composition ofclaim 43, wherein the citral derivative or mixture of citral derivativesis present in admixture with other perfuming ingredients, solvents, oradjuvants of current use in the art of perfuming.
 45. The perfumedarticle of claim 43, in the form of a perfume or cologne, a soap, a bathor shower gel, a shampoo or other hair care product, a cosmeticpreparation, a body deodorant or antiperspirant, an air freshener, afabric detergent or softener or an all-purpose household cleaner.
 46. Abody deodorant or antiperspirant, comprising as a perfuming ingredient acitral derivative, or a mixture of citral derivatives of claim
 34. 47.The body deodorant or antiperspirant of claim 46, wherein the citralderivative or mixture of citral derivatives is present in admixture withother perfuming ingredients, solvents, or adjuvants of current use inthe art of perfuming.
 48. A bleach composition comprising a citralderivative of claim
 34. 49. A beverage comprising a citral derivative ofclaim
 34. 50. The beverage of claim 49, wherein the beverage is selectedfrom the group consisting of beer, malt liquor, lemonade and cola. 51.The beverage of claim 49, wherein the beverage is lemonade.
 52. Aflavored orally-delivered product comprising a citral derivative ofclaim
 34. 53. A method to improve, enhance or modify the odor of aperfuming composition or a perfumed article comprising adding to saidcomposition or said article an effective amount of a citral derivativeor a mixture of citral derivatives of claim
 34. 54. The method of claim53, wherein the citral derivative or mixture of citral derivatives ispresent in admixture with other perfuming ingredients, solvents, oradjuvants of current use in the art of perfuming.
 55. The method ofclaim 54, wherein the citral derivative(s) are present in an amount ofat least 30 percent by weight.
 56. A citral derivative having one of thefollowing formulas:

wherein R₁₋₆ are, independently, selected from the group consisting ofH, C₁₋₅ alkyl, substituted C₁₋₅ alkyl, halo, hydroxy, thiol, thioether,amine, carboxylic acid, ester, nitro, cyano, isocyano, sulfonic acid,urea and thiourea, Z is C(R)₂, R is, independently, H, C₁₋₅ alkyl orC₁₋₅ substituted alkyl, wherein in Formula I, X is —OCH₃, —C(OR)₂H, —CN,—C(═O)CH₃, —NC, —C≡C—R (alkyne), oxime, C(═O)OR⁷ (where R⁷ is a C₁₋₅alkyl), or an oxalate ester, where R is H, C₁₋₅ alkyl or C₁₋₅substituted alkyl, wherein at least one R in the C(R)₂ group is C₁₋₅alkyl or C₁₋₅ substituted alkyl, wherein in Formula II, X is —OCH₃,—C(OR)₂H, —CN, —C(═O)CH₃, —NC, —C≡C—R (alkyne), oxime, C(═O)OR⁷ (whereR⁷ is a C₁₋₅ alkyl), or an oxalate ester, where R is H, C₁₋₅ alkyl orC₁₋₅ substituted alkyl, and in Formula III, X is —C(═O)H, —OCH₃,—C(OR)₂H, —CN, —C(═O)CH₃, —NC, —C≡C—R (alkyne), oxime, C(═O)OR⁷ (whereR⁷ is a C₁₋₅ alkyl), or an oxalate ester, where R is H, C₁₋₅ alkyl orC₁₋₅ substituted alkyl, wherein the substituents on the substitutedalkyl groups are selected from the group consisting of halo, hydroxy,thiol, thioether, amine, carboxylic acid, ester, nitro, cyano, isocyano,sulfonic acid, urea, and thiourea, and wherein the double bond attachedto X can be in the E or Z configuration.
 57. The citral derivative ofclaim 56, wherein at least one R in at least one C(R)₂ group are methyl.58. The citral derivative of claim 56, wherein both R moieties in atleast one C(R)₂ group are methyl.
 59. The citral derivative of claim 56,wherein X is a nitrile, methyl ether or acetal group.
 60. The citralderivative of claim 56, wherein R₁₋₄ are hydrogen.
 61. The citralderivative of claim 56, wherein R₅₋₆ are methyl.
 62. A citral derivativehaving one of the following formulas:

wherein R₁₋₆ are, independently, selected from the group consisting ofH, C₁₋₅ alkyl, substituted C₁₋₅ alkyl, halo, hydroxy, thiol, thioether,amine, carboxylic acid, ester, nitro, cyano, isocyano, sulfonic acid,urea and thiourea, Z is C(R)₂ or saturation at the two carbons to whichit is bound, provided that at least one Z is C(R)₂, R is, independently,H, C₁₋₅ alkyl or C₁₋₅ substituted alkyl, wherein in Formula I, X is—OCH₃, —C(OR)₂H, —CN, —C(═O)CH₃, —NC, —C≡C—R (alkyne), oxime, C(═O)OR⁷(where R⁷ is a C₁₋₅ alkyl), or an oxalate ester, where R is H, C₁₋₅alkyl or C₁₋₅ substituted alkyl, wherein at least one R in the C(R)₂group is C₁₋₅ alkyl or C₁₋₅ substituted alkyl, wherein in Formula II, Xis —OCH₃, —C(OR)₂H, —CN, —C(═O)CH₃, —NC, —C≡C—R (alkyne), oxime,C(═O)OR⁷ (where R⁷ is a C₁₋₅ alkyl), or an oxalate ester, where R is H,C₁₋₅ alkyl or C₁₋₅ substituted alkyl, and Formula III, X is —C(═O)H,—OCH₃, —CN, —C(═O)CH₃, —NC, —C≡C—R (alkyne), oxime, C(═O)OR⁷ (where R⁷is a C₁₋₅ alkyl), or an oxalate ester, where R is H, C₁₋₅ alkyl or C₁₋₅substituted alkyl, wherein at least one R in the C(R)₂ group is C₁₋₅alkyl or C₁₋₅ substituted alkyl, wherein the substituents on thesubstituted alkyl groups are selected from the group consisting of halo,hydroxy, thiol, thioether, amine, carboxylic acid, ester, nitro, cyano,isocyano, sulfonic acid, urea, and thiourea, and wherein the double bondattached to X can be in the E or Z configuration.
 63. The citralderivative of claim 62, wherein at least one R in at least one C(R)₂group is methyl.
 64. The citral derivative of claim 62, wherein both Rmoieties in at least one C(R)₂ group are methyl.
 65. The citralderivative of claim 62, wherein X is a nitrile, methyl ether or acetalgroup.
 66. The citral derivative of claim 62, wherein R₁₋₄ are hydrogen.67. The citral derivative of claim 62, wherein R₅₋₆ are methyl.
 68. Abeverage comprising a compound of claim 56 or
 62. 69. The beverage ofclaim 68, wherein the beverage is selected from the group consisting ofbeer, malt liquor, lemonade and cola.
 70. The detergent compositioncomprising a citral derivative of claim 56 or
 62. 71. A disinfectantcomposition comprising a citral derivative of claim 56 or
 62. 72. Aflavored orally-delivered product comprising a citral derivative ofclaim 56 or
 62. 73. The use of a citral derivative of claim 56 or 62 asa fragrance and/or flavoring.
 74. A method to improve, enhance, ormodify the odor of a perfuming composition or a perfumed articlecomprising adding to said composition or said article an effectiveamount of a citral derivative or a mixture of citral derivatives ofclaim 56 or
 62. 75. The method of claim 74, wherein the citralderivative or mixture of citral derivatives is present in admixture withother perfuming ingredients, solvents, or adjuvants of current use inthe art of perfuming.
 76. The method of claim 74, wherein the citralderivative(s) are present in an amount of at least 30 percent by weight.77. A method for enhancing the stability of citral in acidic orbleaching environments, comprising converting one or both double bondsin citral to cyclopropane or thiirane rings.
 78. The method of claim 77,further comprising converting the aldehyde group in citral to afunctional group selected from the group consisting of —OCH₃, —C(OR)₂H,—CN, —C(═O)CH₃, —NC, ——C≡C—R (alkyne), oxime, C(═O)OR⁷ (where R⁷ is aC₁₋₅ alkyl), or an oxalate ester, where R is H, C₁₋₅ alkyl or C₁₋₅substituted alkyl.